Vinyl resin compositions



United States Patent Office 3,451,961 Patented June 24, 1969 US. Cl. 260-31.8 8 Claims ABSTRACT OF THE DISCLOSURE This invention relates to the use of a plasticizer comprising 7-(2,6,6,8 tetramethyl 4 oxa 3 nonyl)benzyl phthalate in vinyl floor compositions.

This application is a continuation in part of pending application Ser. No. 422,517, filed Dec. 31 1964, now abandoned.

This invention relates to new and useful vinyl resin compositions. In particular, this invention relates to new compositions containing apolymerized vinyl chloride and certain plasticizers therefor.

Hard surface floor coverings are more widely used today than ever before. In particular, plastic floor coverings containing a thermoplastic resin as a binder instead of lino leum cement are finding more and more applications throughout the country. Wider use of plastic floor covering has made it possible to produce the floor covering in a great variety of colors and patterns, many of which are pastel shades or of other light colors; even white floorings, or floorings containing a great deal of white, are in use. X

Use of these light-colored plastic fioorings has pr duced an unexpected problem throughout the industry. Those parts oflight-colored plastic fioorings subjected to heavy trafiic have developed undue brownish or yellowish stains. This phenomenon, known as trafiic staining, now constitutes one of the major problems in the use of lightweight of vinyl resin. However, it is preferred to use from about 20 to about 80 parts by weight of a plasticizer per 100 parts by weight of resin.

7 (2,6,6,8-tetramethyl-4-oxa-3-nonyl)benzyl phthalate can be readily prepared by reacting phthalic anhydride with 2,6,6,8-tetramethyl-4-oxa-3-oxo-nonan-7-o1 to produce a half ester, and thereafter reacting the half ester with a tertiary aliphatic amine and a benzyl halide. The following example serves to further illustrate the preparation of 7-(2,6,6,8-tetramethyl-4-oxa-3-oxo-nonyl)benzyl phthalate. Such example is given for the purpose of illustration only, and is not to be construed as limiting the scope of this invention in any Way.

EXAMPLE I To a suitable reaction vessel having means for the addition and removal of heat, means for measuring the temperature of the reaction mass, means for agitating the reaction mass, means for the addition and removal of solids and liquids, and fitted with a condenser, there are charged 296.2 grams (2.0 mols.) of phthalic anhydride and 436.9 grams (2.02 mols.) of 2,6,6,8-tetramethyl-4- oxa-3-oxo-nonan-7-ol. The mixture is heated to about 124 C., and 2125 grams (2.10 mols.) of triethylamine are added. There is then added 272.15 grams (2.15 mols.) of benzyl chloride. The resultant mixture is held at a temperature of about 138 C. for about one hour and then washed with several water and lye washes. The oil layer from the Washing step is steam sparged and dehydrated at 125-l30 C. at 60-70 mm. Hg. There is obtained 860.8 grams (94.7% of theory) of 7-(2,6,6,8-tetramethyl-4-oxa-3-oxo-nonyl)benzyl phthalate.

The polymerized vinyl chloride resins to be used in the compositions of the present invention may be those low to medium molecular weight resins available in commerce. Illustratiive of such resins are the vinly chloridevinyl acetate copolymers containing about 3% to 5% colored plastic fioorings in heavy traffic areas. The industry has devoted much research time and effort in an attempt to solve this problem, but no satisfactory solution has been found as yet. It has been learned that the trafiic staining problem appears to be related to the plasticizer used with the polymerized vinyl chloride binder in the flooring but, to date, efforts to find a suitable plasticizer which will eliminate or minimize trafiic stain! ing have been unavailing.

It is a primary object of the present invention to supply plasticized polymerized vinyl chloride resin compositions suitable for use in a plastic floor binder, which will reduce or eliminate the traffic staining phenomena. A further object is to present a plastic floor covering binder having increased strength when used in a floor covering,

while at the same time minimizing trafiic staining. A still further object of this invention is to present a plasticizer composition which, when incorporated in vinyl chloride resins, imparts the aforedescribed improved properties.

Other objects and advantages of the invention will be apparent to those skilled in the art from thefollowing detailed description and claims.

In accordance with this invention, it has been found that the above and still further objects are achieved by incorporating in the polyvinyl chloride orpolyvinyl acetatechloride resins of a floor tile composition a plasticizer comprising 7-(2,6,6,8 tetramethyl 4 oxa-3-oxo-nonyl) benzyl phthalate.

Generally speaking, about 5 to about 100 partsby weight of plasticizer can be used for each 100 parts by'" vinyl acetate, made by the Bakelite Company and bearing the designations VYMF and VYVF. The copolymers containing about 13% vinyl acetate, such as those designated VYNW and VY'I-IH, are also suitable. Straight polyvinyl chloride resins, such as those designated as GEON and OPALON resins, particularly GEON 12 1, GEON 126 and OPALON 630, are suitable. Qther vinyl chloride resins found to be suitable include those designated as QYNW, EXON 666, OPALON 410 and OPALON 440. Mixtures of one of the homopolymers and a copolymer will frequently be used. The most significant property of the polymerized vinyl chloride resin suitable for use in the compositions of the present invention is that of yield of a hard, tough and otherwise desirable surface covering material after being plasticized and admixed with suitable fillers and other ingredients.

Generally speaking, it is contemplated that the composition to be used as a binder will comprise about 50% to about 25% by Weight of the Wearing surface composition of the floor covering. The binder is admixed with filler, including pigment, in such proportions that the filler comprises about 50% to about by Weight of the compositions. When the filler content is below about 50%, pattern content may be difficult. When more than about 75% by weight of filler is present, the physical properties of the finished surface covering materials do not measure up to the desired standards in floor covering art. The filler material may be organic or inorganic, or mixtures thereof. The filler often contains a filler material. If the flooring is destined to be installed benzoate and 2-ethylhexyl-p-oxybenzoate; hydrocarbons, below grade, then it is preferred that the filler system for example, polyphenyls such as o-terphenyl, p-terconsist of inorganic fillers, either fibrous, non-fibrous or phenyl, m-terphenyl and mixtures thereof, and partially both. Such a filler system is insensitive to the alkaline hydrogenated terphenyl; chlorinated polyphenyls such moisture conditions encountered on below-grade or noas chlorinated o-terphenyl, p-terphenyl, m-terphenyl and brade installations. Also included in the filler component mixtures thereof and chlorinated biphenyl; alkylated are small but effective amounts of lubricants and detachpolyphenyls such as isopropyl biphenyl, diisopropyl biifying agents, such as stearic acid, paraiiin wax, ceresin phenyl and isopropyl terphenyl; alkyl aryl hydrocar- WaX, Ol ic a id and Laurie acid. Snythetic rubber, such bons such as triethyl benzene, tetraethyl benzene, hexaas the butadiene styrene copolymers or the butadiene ethyl benzene, diisopropylbenzene, triisopropyl benzene, acrylonitrile copolymers, may be added. The addition of di-n-propyl benzene, di-n-butyl benzene and partially these rubbers renders the composition sulfur-curable, hydrogenated alkyl aryl hydrocarbon (partially hywhereby vulcanizing agents and the curing accelerators drogenated terphenyl and the partially hydrogenated may then be added to the filled composition. Thus, there alkyl aryl hydrocarbon are marketed as HB-40 and may be added sulfur, or sulfur-containing compounds, HB- respectively by Monsanto Chemical Co.)', aryl along with various vulcanization accelerators, as, for exalkanes such as monophenyl decane, monophenyl doample, zinc phenyl ethyl dithiocarbamate, diethyl dithiodecane, monophenyl pentadecane and monophenyl octa- Cafbamate, Zihc P PY dithiocalbamate, Zinc dibthyl decane and the like and mixtures thereof; chlorinated dithiocflfbamate, p y ghahadihe, tetraethyl thhlfam aryl alkanes; and chlorinated paraffin hydrocarbons of disulfide and tetramethyl thiuram disulfide. Stabilizers 20 the composition in the range of C H to C H In antioxidants Such as hydroqllinohe, -p yl p such compositions wherein conventional prior art plastithylamine, 'p y fip y y cizers are incorporated, there is employed from about 0.3 ene-bistorthohydroxv benzamide), sodium acid ph part to about 10 parts by Weight of 7-(2,6,6,8-tetraphate, dibutyl tin dilaurate and others known in the art, methyl-4-oxa-3-oxo-nonyl) benzyl phthalate per part by y be used The total amount of the compounding weight of the complementary plasticizer or mixtures agents, exclusive of the fibrous and non-fibrous filler, th i generally run P {0 about 10% y Weight 0f In order to demonstrate some of the desirable and un- C-onventional prior art plasticizing agents and mixtures t d properties displayed by the plasticizer compothefeof can be incorporated into the Present p sition of this invention, a number of resinous compositions. Such compounds include: Phthalate esters such as tion w r re ared and subjected to various test prodimethyl phthalate, diethyl phthalate, dibutyl phthalate, dur

diisobutyl Phthalate, blltyl octyl Phihalate, diheXyl In a first series of tests, a polyvinyl chloride resin was I dioctyl Phthalate, Q- y y Phlhalate, mixed with several plasticizers shown in Table I wherein octyl debyl Phthalflte, dhsbdbbyl Phlhalate, ditl'idecyl all parts are parts by weight. Samples containing a 40% Phthalate, y CYCIOheXYI Phihalate, butyl behlyl concentration of plasticizer were then checked for low Phthalate, di(Ce11oso1ve) Phthalatb, di(blltyl Cellosolvfi) temperature flexibility, volatility, hardness, Water absorp- Phthalate, mohobutyl P y butyl glycolaie 65161, tion and kerosene extraction in accordance with A.S.T.'M. mohoethyl P y ethyl glycblatb ester and likb; procedures. Results of these tests are summarized in phosphate esters such as cresyl diphenyl phosphate, Table 11 Parts phenyl dicresyl phosphate, tricresyl phosphate; the liquid 1 m 100 alkyl diaryl phosphates wherein the alkyl group con- PO Y i on e 1 tains from 6 to 14 carbon atoms and the aryl groups ii are phenyl or cresyl or mixtuers thereof, e.g., octyl diii i ff 15 phenyl Z-ethylhexyl dicresyl phosphates; the dialkyl aryl 3.1mm 8 2- 5.17; 2 5 phosphates such as Z-ethylhexyl butyl phenyl, decyl isog mmm s a amyl cresyl phosphates, etc., the liquid esters of dicari (3 boxylic acid such as dibutyl sebacate, dihexyl adipate, E ia: f-"T di(butyl Cellosolve) adipate, and the like; epoxidized pom 1Z5 59y 01 vegetable oils such as epoxidized soya oils; glycol benzoghoibe and g g i given in accompanying tablesates such as diethylene glycol dibenzoate, dipropylene are i s ywelg glycol dibenzoate, triethylene glycol di-benzoate, pen- After the usual mixing and sheet-forming operations, taerythritol tetrabenzoate, 3-methyl-1, S-pentanediol ditest installations were made wherein white floor coverings TABLE I.PLASTICIZER COMPOSITION Butyl benzyl phthalate Di-2-ethyl hexyl phthalate Butyl octyl phthalate 7-(2,6,6,8-tetramethyl-4-oxa-3-ox onyl) ban lphthala Dimethy1phthalate. 10 20 LIB-40 4. 10 20 Ditrideeyl phthalate--- Diethyl phthalate Diisobutyl phthalate 20 l Partially-hydrogenated terphenyl.

TABLE II Hardness Shore A Water Absorption Kerosene Volatility, xt Per- 1. t, Percent Before After Percent Percent cent Piss.- Plasticizer C Plas. Loss Vol. Vol. las. Loss Abs. Loss in the form of sheets having the above formulation were installed in heavy traffic areas. After three months of use, the flooring was inspected for staining. The compositions containing plasticizers l and 2 were appreciably darker and carried a more heavy, yellow, permanent tratfic stain than the composition containing plasticizers 4, 5, 6 and 7.

In order to assess quantitative values, additional stain tests were made with compositions containing various plasticizers selected from plasticizers 1 through 17 of Table I. A 0.5% Du Pont oil-soluble yellow dye dissolved in kerosene was used as the stainant in the examples shown in Table III. The stainant remained in contact with the plasticized vinyl tile samples for thirty minutes. In Test A, the intensity of stain was measured on a G.E. recording spectrophotometer, Model 701513 30 G62. This instrument determined the tristimulus values (XYZ) for which dominant wave lengths and the excitation purity of the hue of color are calculated in accordance with ICI (International Committee of Illumination) method. The excitation purity value is used to compare one tile with another tile, wherein 0% purity equals pure white light and 100% purity equals a pure spectral color, such as yellow. The lower purity value indicates a greater stain resistance. PHR represents the parts of plasticizer used per 100 parts of resin.

The visual rating obtained in Test B employed a scale of 0 to 10. The value of was given to the composition containing diisodecyl phthalate which showed the least stain resistance. Lower numbers show greater stain resistance, a value of 0 being an indication of no staining. PHR represents the parts of plasticizer used per 100 parts of resin.

TABLE III Test A, Percent Test B Plasticizer Phr. Purity Visual Rating The foregoing table demonstrate the remarkable stain resistance etfect which can be obtained using 7-(2,6,6,8- tetramethyl-4-oxa-3-oxo-nonyl) benzyl phthalate alone and in combination with conventional vinyl resin plasticizers in floor tile formulations.

While this invention has been described with respect to certain specific embodiments, it is not so limited. It is to be understood that variations and modifications thereof may be made without departing from the spirit and scope of the invention.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A composition of matter comprising a polymerized vinyl chloride resin selected from the group consisting of polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, and mixtures thereof, and from about 5 to about 100 parts by weight per 100 parts by weight of resin of a plasticizer consisting essentially of 7-(2,6,6,8-tetramethyl- 4-oxa-3-oxo-nonyl) benzyl phthalate.

2. A composition as defined in claim 1 wherein said resin is polyvinyl chloride.

3. A composition as defined in claim 1 wherein from about 20 to about parts by weight of a plasticizer consisting essentially of 7-(2,6,6,8-tetramethyl-4-oxa-3-oxononyl) benzyl phthalate are employed per parts by weight of resin.

4. A composition of matter comprising polyvinyl chloride and from about 20 to about 80 parts by weight per 100 parts by weight of polyvinyl chloride of a mixture of 7 (2,6,6,8 tetramethyl 4-oxa-3-oxo-nonyl) benzyl phthalate and butyl benzyl phthalate, from about 0.3 part to about 10 parts of the former being employed per part of the latter.

5. A composition as defined in claim 4 wherein about one part of 7-(2,6,6,8-tetramethyl-4-oxa-3-oxo-nonyl) benzyl phthalate is employed per part of butyl benzyl phthalate.

6. A composition as defined in claim 4 wherein about 3 parts of 7-(2,6,6,8-tetramethyl-4-oxa-3-oxo-nonyl) benzyl phthalate are employed per part of butyl benzyl phthalate.

7. A composition of matter comprising polyvinyl chloride and from about 20 to about 80 parts by weight per 100 parts by weight of polyvinyl chloride of a mixture of 7-(2,6,6,8-tetramethyl-4-oxa-3-oxo-nonyl) benzyl phthalate and dimethyl phthalate, from about 4 parts of the former being employed per part of the latter.

8. A composition of matter comprising polyvinyl chloride and from about 20 to about 80 parts by weight per 1 00 parts by weight of polyvinyl chloride of a mixture of 7-(2,6,6,8-tetramethyl-4-oxa-3-oxo-nonyl) benzyl phthalate and diisobutyl phthalate, from about 4 parts of the former being employed per part of the latter.

References Cited UNITED STATES PATENTS 3,090,763 5/ 1963 Hillier 260-318 3,152,096 10/1964 Darby 26030.4 3,160,599 12/ 1964 Scullin 26031.'6 3,21 1,561 10/1965 Gearhart et al. 260-316 3,211,689 10/1965 Darby 260-31.4 3,318,835 5/1967 Hagemeyer et a1. 260-31.6

FOREIGN PATENTS 629,888 1071963 Belgium.

MORRIS LIEBMAN, Primary Examiner. HENRY S. KAPLAN, Assistant Examiner.

US. Cl. X.R. 260-322 

